Chemical Kinetics. System LENGTH: VOLUME MASS Temperature. 1 gal = 4 qt. 1 qt = in 3. 1 L = qt. 1 qt = L

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1 Chemical Kinetics Practice Exam Chemical Kinetics Name (last) (First) Read all questions before you start. Show all work and explain your answers to receive full credit. Report all numerical answers to the proper number of significant figures. By signing your signature above you agree that you have worked alone and neither give nor received help from any source. Keep your eyes on your own paper at all times System LENGTH: VOLUME MASS Temperature English: 1 ft = 12 in 1 gal = 4 qt 1 lb = 16 oz T F = 1.8T C mile = 5280 ft 1 qt = in 3 1 ton = 2000 lb 1 yd = 3 ft SI- English: 1 in = 2.54 cm 1 mi = km 1 L = qt 1 qt = L 1 lb = g 1 oz = g T C = (T F 32) 1.8 Misc. info 1 mole = R = J/ mol K or L atm/mol K Rates of Reaction rate = Δ[A] /Δ t = - Δ [react] /Δ t = Δ [prod] /Δ t Rate laws (Order of reaction) initial rate = k [A] x [B] y [C] z... Overall order = x + y + z +... Conc. vs. Time dependence Zeroth Order Conc. vs. Time straight line. rate = k [A] = [A]o - kt Half life; t1/2 = [A]o / 2 k First Order [A] = [A]o exp{- kt) ln[conc.] vs. Time straight line rate = k [A] ln[a] = ln[a]o - kt Half life; t1/2 = / k Second Order 1/[Conc.] vs. Time straight line rate = k [A] 2 or k [A] [B] 1/[A] = 1/[A]o + kt Half life; t1/2 = 1 / k [A]o Temperature vs. Rate dependence k = A exp {-E a /RT} ln k = ln A - (E a / R) 1/T ln(k) vs. 1/T straight line. ln(k 1/k 2) = (E a / R) (1/T 2-1/T 1)

2 Multiple -choice. Show work for partial credit. 1 Which of the following statement is true? a) The activation energy of a reaction increases with increasing temperature. b) The slowest step in a mechanism will always determine the rate of a reaction. c) A catalyst not only changes the activation energy of a reaction, it also changes ΔH rxn. d) All of these statements are true. 2 A plot of [A] -1 vs., time is most likely a a) Arrhenius equation b) second order reaction c) first order reaction d) zeroth order reaction 3 If the heat of reaction is endothermic, which of the following is always true? a ) the reaction is fast b) the reaction is slow c) the energy of the reactants is greater than the products d) the energy of the reactants is lower than the products 4 The rate of a reaction is not influenced by: a) concentration of reactant b) Catalyst c) Energy of Reactant d) stirring of chemicals 5 The pre-exponential factor in the Arhenius equation takes in to account: a) The steric factor b) The activation energy c) The energy of the reaction d) The Maxwell-Boltzmann curve.

3 6 The reaction: 2I - (aq) + S2O8 2- (aq) I2(aq) + 2SO4 2- (aq) was studied at 25 C. The following results were obtained [ I - ] o (M) [S2O8 2- ] (M) Initial Rate (M/s) i) Determine the rate law. i) Rate = k [I ] x [S 2 O 8 2 ] y = k [I ] 0 [S 2 O 8 2 ] 2 ii) What is the rate constant using experiment # 2 iii) What is the molecularity of this reaction? iv) Calculate the half-life using the data from Experiment2 Rate(expt2) = k [I ] 0 [S 2 O 8 2 ] 2 ii) = k [.040] 0 [.040] 2 k = 3.125x [.040] 2 = iii) Bimolecular since Order = 2 = iv) 1 t 12 = k A o [ ] = [.040M] =12,800 s 7 Determine if the statements below are true or false then write a convincing statement to justify your answer. a) At a given temperature, all molecules posses the same kinetic energy False. The MB distribution plot shows that any given temperature molecules will have a range of kinetic energy with the average centered at the U rms. b) Reactant molecules must collide with greater energy than the activation energy in order to change to product molecules. False. Not only must the molecules collide with sufficient energy to overcome the activation energy, they molecules must also have the right orientation (steric factor). c) The activation energy of a reaction is not dependent on the temperature. True. The E act is a function of the mechanism of the reaction, which is a function of the chemicals that are involve in the reaction. Remember in the Crystal Violet Experiment that E act was the same whether the data was collected at high temperature or low temperature. In fact the temperature data was used to determine E act. d) A catalyst increases the rate by increasing collision frequency. False. A catalyst changes the mechanism, which alters (lowering) the Eact, thereby increasing the rate of the reaction. The reason the reaction rate increases is because Eact decreases. Collision Frequency may have been altered but it is not the primary reason for the rate change. 8 Explain using a Maxwell-Boltzmann Distribution curve why an exothermic reaction favors an increase of the reverse reaction at higher temperature even though according to the Kinetic Molecular Theory, the rate of a reaction increases with increasing temperature. For an exothermic reaction, if the temperature is increase, the percentage of the product molecules is greater than that of the reactant that surpasses the activation Energy. Therefore more products will return to reactants therefore shifting the reaction to the left.

4 9 Most reaction occurs by a series of steps. The energy profile shown below is a three-step mechanism for the reaction of NO with H2. i) 2NO N 2 O 2 fast ΔH 1 = + 20 kj Eact 1 = 50 kj E 1 = 50 kj (Transition state) ii) N 2 O 2 + H 2 N2O + H2O slow ΔH 2 = + 30 kj Eact 2 = E 2 = 100 kj iii) N2O + H 2 N 2 + H2O fast ΔH 3 = - 10 kj Eact 3 = 30 kj E 3 =? Place answers to questions ii, iii, iv, & vi. E (NO) = 0_kJ E(N 2 O 2 )= 20 kj Eact2 = 80 kj E 3 = 80 kj ΔHrxn= 40 kj Eact(f)= 100 kj Eact(r)= 60 kj Label the graph above placing the chemical specie along the reaction profile diagram and then answer the following: i) What is the overall stoichiometry and what are the intermediate and the catalyst (if any)? 2NO + 2H 2 N 2 + 2H 2 O, Intermediate = N 2 O 2, N 2 O, Catalyst = None ii) What are the energies of NO and N2O2 according to the graph above? E NO = 0 kj E N2O 2 = 20 kj iii) What are the energies of Eact2 and E 3? Eact2 = 80 kj E 3 = 80 kj iv) What is the energy of the overall reaction, DHrxn? ΔHrxn = + 40 kj v) Is the reaction endothermic or exothermic? ΔHrxn = + 40 kj > 0, Endothermic vi) What are the activation energies for the overall forward Eact(f), and overall reverse Eact(r), reactions? Eact(f) = 100 kj E act(r) = 60 kj vii) What are the rate law and the molecularity for this reaction? Rate = k [N 2 O 2 ] [H 2 ], but N 2 O 2 is an intermediate thus K eq = [N 2 O 2 ] / [NO] 2 Thus, Rate = k Keq [NO] 2 * [H 2 ] = K [NO] 2 * [H 2 ], termolecular viii) If the pre-exponential factor is , what is the rate constant (include units) for this reaction at 600K? k = A exp [-E a /RT}, thus k = exp [-100,000 J / J mol K -1 * 600 K} k = 25 M -2 / s ix) What temperature is required to raise the rate constant to 250? (units are not shown here) k = A exp [-E a /RT}, lnk = lna - E a /RT, T = E a /R(lnK lna), T = 678 K x) If the catalyzed reaction is ten times faster than the uncatalyzed reaction, what is the rate of disappearance of the reactant for the catalyzed reaction? You may assume that you are using the methods of initial rates in which the concentration of all chemicals are 1.0 M. T= 600 K Rate = 250 M / s

5 10 The reaction of hydrogen with iodine has the following accepted mechanism: (1) I2 (g) 2I (g) fast (2) H2(g) + I (g) H2I (g) fast (3) H2I (g) + I (g) 2HI (g) slow What is the rate law for this reaction? 11 Consider the following reaction energy diagram: i) How many elementary steps in the reaction mechanism? 170 kj A C ii) Which step is rate limiting? i.e. 1st, 2nd, 3rd, 4th,... iii) Is the overall reaction exothermic or endothermic? iv) What is the energy of the reaction (kj)? v) What is the activation energy (kj) for the reverse rxn? 100 kj 45 kj 0 kj - 60 kj A B C vi) What is the Eact (kj) for the rate determining step?

6 12 A theoretical reaction: A + B C, has the following initial rate data shown below. Expt. # [A] M [B] M -Δ [A] / Δt M/s 1 (300K) x (300K) x (300K) x (300K) x (600K) i) Determine the complete rate law for the reaction including the rate constant with proper units. ii) What is the activation energy (Ea in kj) for this reaction and the frequency factor (A).

7 13 A slightly bruised apple will rot extensively in about 4 days at room temperature (20 C). If it is kept in the refrigerator at 0 C, the same extent of rotting takes about 16 days. What is the Eact (kj) for the rotting reaction?

8 14 Determine if the statements are true or false. Give a reasonable explanation to support or refute these statements. i) At a given temperature, all molecules posses the same kinetic energy. ii) The higher the activation energy of a reaction, the slower the rate of the reaction. iii) If reactant molecules collide with greater energy than the activation energy, products are formed automatically. iv) Exothermic reaction have faster rates than endothermic reactions. v) The activation energy of a reaction is lowered by a catalyst. vi) The enthalpy change for a reaction is lowered by a catalyst

1.8. ΔG = ΔH - TΔS ΔG = ΔG + RT ln Q ΔG = - RT ln K eq. ΔX rxn = Σn ΔX prod - Σn ΔX react. ΔE = q + w ΔH = ΔE + P ΔV ΔH = q p = m Cs ΔT

1.8. ΔG = ΔH - TΔS ΔG = ΔG + RT ln Q ΔG = - RT ln K eq. ΔX rxn = Σn ΔX prod - Σn ΔX react. ΔE = q + w ΔH = ΔE + P ΔV ΔH = q p = m Cs ΔT ThermoDynamics Practice Exam Thermodynamics Name (last) (First) Read all questions before you start. Show all work and explain your answers to receive full credit. Report all numerical answers to the proper

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1.8. ΔG = ΔH - TΔS ΔG = ΔG + RT ln Q ΔG = - RT ln K eq. ΔX rxn = Σn ΔX prod - Σn ΔX react. ΔE = q + w ΔH = ΔE + P ΔV ΔH = q p = m Cs ΔT

1.8. ΔG = ΔH - TΔS ΔG = ΔG + RT ln Q ΔG = - RT ln K eq. ΔX rxn = Σn ΔX prod - Σn ΔX react. ΔE = q + w ΔH = ΔE + P ΔV ΔH = q p = m Cs ΔT ThermoDynamics Practice Exam Thermodynamics Name (last) (First) Read all questions before you start. Show all work and explain your answers to receive full credit. Report all numerical answers to the proper

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